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When it comes to lipstick, Anne Hathaway was a prodigy. "My first play at the stuff was in my mother's bathroom," she has said. "I wanted big lips, so I took her red lipstick and proceeded to run it all over my face. I was five." The 31-year-old, Oscar-winner has remained a fan of the classic lip, drawing comparisons to Hollywood legends. "Her porcelain skin and amazing features give her an Ava Gardner quality," says her stylist Rachel Zoe. With kindergarten—and Mom's hand-me-downs—long behind her, Hathaway is a true 21st-century style-setter.

1997: The freshman at Millburn High School in New Jersey was a natural beauty. (Photo: Seth Poppel/Yearbook LibrarySee More at InStyle.com

The New Jersey native kicked off her career with the TV series "Get Real." "I went through all kinds of frosts and glosses during my teens," Hathaway has said of her youthful makeup look. (Photo: Walter Weisman/Globe)See More at InStyle.com

Thick face-framing bangs gave her hair a new dimension—a much better one than the big blond nest she had as Lureen in "Brokeback Mountain." (Photo: Graham Whitby-Boot/Allstar/Globe)See More at InStyle.com

Frederic Fekkai hairstylist Adir Abergel created a sophisticated and modern updo for the Oscars. Inspired by the Edwardian era, he swept hair over her ears instead of slicking it behind them for a relaxed, elegant style. (Photo: Jennifer Graylock/AP Photo)See More at InStyle.com

For the premiere of her movie "One Day," Hathaway wore a gold embroidered Alexander McQueen gown. "The dress had great structure, so we kept her makeup cute and young," says Chanel makeup artist Kate Lee. She started with a sheer shadow to define the contours of the starlet's eyes. "I drew a thin line of black eye pencil along the base of the lashes and inside the waterline for an ink pot effect," she explains. Next, Lee glided a small natural fiber brush with a crème shadow in deep charcoal out to the corners, blending a tiny amount under the eyes to soften the shape. (Photo: Gregory Pace / BEImages)See More at InStyle.com

"I wanted to create a glamorous, high-drama look appropriate for a New York movie premiere," hairstylist Adir Abergel said of Hathaway's sleek style. "The diagonal side part is a dramatic look within itself, but paired with Anne's short hairstyle, the drama factor was taken up a notch." While the star's strands were still wet, Abergel formed a side part that started at the corner of her eyebrow, sectioning her hair at an angle for a dramatic effect. He added texturizer to boost volume, and after a quick pass with the blow-dryer, he slicked on a hair gel to impart a sleek, mirror-like texture: "The final result was a smooth, high-shine hairstyle that brought the entire look together, and gave it a super-chic finish." (Photo: Jim Spellman/WireImage)See More at InStyle.com

To allow her embellished Chanel gown to take center stage at the Golden Globes, Hathaway's makeup look was kept neutral—save for a radiant complexion and rose-hued lip. "Anne's look was elegant, but still youthful and light. I felt that the makeup should mirror this," said her makeup artist Kate Lee. "I concentrated on making the complexion as tactile as possible, and added a dash of blue-pink to the lips as a focal point." Lee created a flawless canvas with Chanel's Vitalumiere Aqua foundation and the Perfection Lumiere Long-Wear Foudation, then finished with Chanel's Rouge Allure Lip Color in Seduisante on Hathaway's lips. "It's the perfect pink for a perfect pout," Lee added. (Photo: Alberto Rodriguez/NBC/NBC via Getty Images)See More at InStyle.com

The only thing more shocking than Hathaway's pixie cut might have been when she appeared on the red carpet at the 2013 Met Gala with blonde hair that was so light, it looked to have been dyed with hydrogen peroxide. "I decided to go for a look that's glam and edgy, yet youthful and fun," her hairstylist Sascha Breuer said. "We decided to take her hair to the next level: A cool platinum blonde color!" Mission accomplished! (Photo: Gregory Pace/BeImages)See More at InStyle.com

At Elyse Walker's Pink Party in Los Angeles, Hathaway went back to a darker shade and swept her bangs to the side. She paired her new do with a fresh face and simple pink lip. (Photo: Kevan Brooks/Admedia/SIPA USA)See More at InStyle.com